Acylatign agents and dispersants for lubricating oil and fuels

ABSTRACT

Hydrocarbyl substituted carboxylic compositions and derivatives thereof useful as additives for lubricating oil and fuel compositions. Carboxylic composition are derived from (A) an olefinically unsaturated hydrocarbon, said hydrocarbon having at least one allylic hydrogen atom, and (B) an α,β-unsaturated carboxylic compound prepared by reacting
         (1) an active methylene compound of the formula 
                 
    and   (2) a carbonyl compound of the general formula 
                 
    wherein R a  is H or hydrocarbyl and R b  is a member of the group consisting of H, hydrocarbyl and 
                 
    wherein each R′ is independently R or OR and each R is, independently, H or a hydrocarbyl group; and lower alkyl acetals, ketals, hemiacetals and hemiketals of the carbonyl compound (2). Carboxylic derivative compositions are obtained by reacting the carboxylic compositions with a reactant selected from the group consisting of (a) amines characterized by the presence within their structure of at least one condensable H—N&lt; group, (b) alcohols, (c) reactive metal or reactive metal compounds, and (d) a combination of two or more of any of (a) through (c), the components of (d) being reacted with the carboxylic composition simultaneously or sequentially, in any order.

This application claims the benefit of Provisionsl Application No.60/213,347, filed Jun. 22, 2000.

FIELD OF THE INVENTION

This invention relates to hydrocarbyl substituted carboxyliccompositions and derivatives prepared therefrom. The carboxyliccompositions and derivatives are useful as detergents and dispersantsfor lubricating oil and fuel compositions.

BACKGROUND OF THE INVENTION

Numerous types of additives are used to improve lubricating oil and fuelcompositions. Such additives include, but are not limited to dispersantsand detergents of the ashless and ash-containing variety, oxidationinhibitors, anti-wear additives, friction modifiers, and the like. Suchmaterials are well known in the art and are described in manypublications, for example, Smalheer, et al, “Lubricant Additives”,Lezius-Hiles Co., Cleveland, Ohio, USA (1967); M. W. Ranney, Ed.,“Lubricant Additives”, Noyes Data Corp., Park Ridge, N.J., USA (1973);M. J. Satriana, Ed., “Synthetic Oils and Lubricant Additives, Advancessince 1977”, Noyes Data Corp., Park Ridge N.J., USA (1982), W. C.Gergel, “Lubricant Additive Chemistry”, Publication 694-320-65R1 of theLubrizol Corp., Wickliffe, Ohio, USA (1994); and W. C. Gergel et al,“Lubrication Theory and Practice” Publication 794-320-59R3 of theLubrizol Corp., Wickliffe, Ohio, USA (1994); and in numerous UnitedStates patents, for example Chamberlin, III, U.S. Pat. No. 4,326,972,Schroeck et al, U.S. Pat. No. 4,904,401, and Ripple et al, U.S. Pat. No.4,981,602.

Many such additives are derived from carboxylic reactants, for example,acids, esters, anhydrides, lactones, and others. Specific examples ofcommonly used carboxylic compounds used as intermediates for preparinglubricating oil additives include alkyl-and alkenyl substituted succinicacids and anhydrides, polyolefin substituted carboxylic acids, aromaticacids, such as salicylic acids, and others. Illustrative carboxyliccompounds are described in Meinhardt, et al, U.S. Pat. No. 4,234,435;Norman et al, U.S. Pat. No. 3,172,872; LeSuer et al, U.S. Pat. No.3,454,607, and Rense, U.S. Pat. No. 3,215,707.

Such carboxylic acids can be prepared by thermally reacting an aliphatichydrocarbon or halogenated aliphatic hydrocarbon with unsaturated acidsor acid derivatives at temperatures above about 200° C. The hydrocarbontypically is an olefin polymer such as polypropene or polybutene havingnumber average molecular weights generally above 200. The rate ofconversion of such reactions, however, is low and attempts to improvethe conversion rate by increasing the reaction temperature and/or usingsuper-atmospheric pressure results in degradation of maleic anhydride tocarbon dioxide, water and tar-like solids

Many carboxylic intermediates used in the preparation of lubricating oiladditives contain chlorine. One technique which has been used forimproving the conversion rate, particularly when using aliphatichydrocarbon alkylating agents, involves carrying out the reaction in thepresence of chlorine. In some instances, high temperatures and longreaction times still are required.

While the amount of chlorine present is often only a small fraction ofthe total weight of the intermediate, the chlorine frequently is carriedover into the carboxylic derivative which is desired as an additive. Fora variety of reasons, including environmental reasons, the industry hasbeen making efforts to reduce or to eliminate chlorine from additivesdesigned for use as lubricant or fuel additives. The matter of chlorinecontent in additives is discussed in numerous patents including U.S.Pat. Nos. 5,356,552; 5,370,805; 5,445,657 and 5,454,964.

Accordingly, it is desirable to provide low chlorine or chlorine freeadditives for use in lubricants and fuels. While hydrocarbyl groupsubstituted carboxylic compositions of this invention may be preparedemploying the use of added chlorine during the reaction, the(α,β-unsaturated carboxylic compounds used to prepare the carboxyliccompositions tend to react more readily, and with less attendantgeneration of tar and other decomposition products than previouslyemployed unsaturated carboxylic compounds such as maleic anhydride.

In industry, it is also desirable to have available a wide variety ofreactants available to prepare compositions. Materials shortages, costs,etc. contribute to uncertainties in the industry. These uncertaintiescan be relieved when more than a limited number of types raw materialsare available to a manufacturer. The compositions of this invention areprepared employing raw materials that are different from, and are notsuggested by, traditionally used raw materials.

SUMMARY OF THE INVENTION

This invention relates to carboxylic compositions and derivativesthereof. The carboxylic compositions are useful as intermediates forpreparing derivatives for use as lubricant and fuel additives. Both thecarboxylic compositions and the derivatives thereof find utility asadditives for lubricating oil and fuel compositions. Hydrocarbyl groupsubstituted carboxylic composition are derived from (A) an olefinicallyunsaturated hydrocarbon, said hydrocarbon having at least one allylichydrogen atom, and (B) an α,β-unsaturated carboxylic compound preparedby reacting (1) an active methylene compound of the formula

and (2) a carbonyl compound of the general formula

wherein R^(a) is H or hydrocarbyl and R^(b) is a member of the groupconsisting of H, hydrocarbyl and

wherein each R′ is independently R or OR and each R is, independently, Hor a hydrocarbyl group; and lower alkyl acetals, ketals, hemiacetals andhemiketals of the carbonyl compound (2). Carboxylic derivativecompositions are obtained by reacting the hydrocarbyl substitutedcarboxylic compositions with a reactant selected from the groupconsisting of (a) amines characterized by the presence within theirstructure of at least one condensable H—N< group, (b) alcohols, (c)reactive metal or reactive metal compounds, and (d) a combination of twoor more of any of (a) through (c), the components of (d) bring reactedwith the hydrocarbyl substituted carboxylic composition simultaneouslyor sequentially, in any order.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

As used herein, the terms “hydrocarbon”, “hydrocarbyl” or “hydrocarbonbased” mean that the group being described has predominantly hydrocarboncharacter within the context of this invention. These include groupsthat are purely hydrocarbon in nature, that is, they contain only carbonand hydrogen. They may also include groups containing substituents oratoms which do not alter the predominantly hydrocarbon character of thegroup. Such substituents may include halo-, alkoxy-, nitro-, etc. Thesegroups also may contain hetero atoms. Suitable hetero atoms will beapparent to those skilled in the art and include, for example, sulfur,nitrogen and oxygen. Therefore, while remaining predominantlyhydrocarbon in character within the context of this invention, thesegroups may contain atoms other than carbon present in a chain or ringotherwise composed of carbon atoms.

In general, no more than about three non-hydrocarbon substituents orhetero atoms, and preferably no more than one, will be present for every10 carbon atoms in the hydrocarbon or hydrocarbon based groups. Mostpreferably, the groups are purely hydrocarbon in nature, that is theyare essentially fire of atoms other than carbon and hydrogen.

Throughout the specification and claims the expression oil soluble ordispersible is used. By oil soluble or dispersible is meant that anamount needed to provide the desired level of activity or performancecan be incorporated by being dissolved, dispersed or suspended in an oilof lubricating viscosity. Usually, this means that at least about 0.001%by weight of the material can be incorporated in a lubricating oilcomposition. For a further discussion of the terms oil soluble anddispersible, particularly “stably dispersible”, see U.S. Pat. No.4,320,019 which is expressly incorporated herein by reference forrelevant teachings in this regard.

It must be noted that as used in this specification and appended claims,the singular forms also include the plural unless the context clearlydictates otherwise. Thus the singular forms “a”, “an”, and “the”include. the plural; for example “an amine” includes mixtures of aminesof the same type. As another example the singular form “amine” isintended to include both singular and plural unless the context clearlyindicates otherwise.

Olefinically Unsaturated Hydrocarbon

The hydrocarbyl group substituted carboxylic compositions of thisinvention are derived from olefinically unsaturated hydrocarbons havingat least one allylic hydrogen atom. As used herein, the term allylichydrogen atom refers to a hydrogen atom on a saturated aliphatic carbonatom alpha to an olefinic double bond, i.e., the hydrogen atom in thegroup of formula

The olefinically unsaturated hydrocarbon typically contains at leastabout 8 carbon atoms, often at least about 30 carbon atoms andpreferably at least about 50 carbon atoms, up to about 800, frequentlyup to about 400, often up to about 200 and preferably up to about 150carbon atoms. Often, the olefinically unsaturated hydrocarbon comprisesat least one polyolefin. The olefinically unsaturated hydrocarbon has{overscore (M)}_(n) ranging from about 300 to about 10,000, often{overscore (M)}_(n) ranging from about 300 to about 8,000 and morefrequently from about 300 to about 5,000. In another embodiment, theolefinically unsaturated hydrocarbon has {overscore (M)}_(n) rangingfrom about 300, often from about 900 to about 2500. Preferred {overscore(M)}_(n) values often depend upon the nature of the olefinicallyunsaturated hydrocarbon as set forth in greater detail hereinbelow.

Molecular weights of the olefinically unsaturated compounds aredetermined using well known methods described in the literature.Examples of procedures for determining the molecular weights are gelpermeation chromatography (GPC) (also known as size-exclusionchromatography), light scattering, and vapor phase osmometry (VPO). TheGPC technique employs standard materials against which the samples arecompared. For best results, standards that are chemically similar tothose of the sample are used. For example, for polystyrene polymers, apolystyrene standard, preferably of similar molecular weight, isemployed. When standards are dissimilar to the sample, generallyrelative molecular weights of related polymers can be determined. Forexample, using a polystyrene standard, relative, but not absolute,molecular weights of a series of polymethacrylates may be determined.These and other procedures are described in numerous publicationsincluding:

P. J. Flory, “Principles of Polymer Chemistry”, Cornell University Press(1953), Chapter VII, pp 266-316, and

“Macromolecules, an Introduction to Polymer Science”, F. A. Bovey and F.H. Winslow, Editors, Academic Press (1979), pp 296-312.

W. W. Yau, J. J. Kirkland and D. D. Bly, “Modern Size Exclusion LiquidChromatography”, John Wiley and Sons, New York, 1979.

In one preferred embodiment, the olefinically unsaturated hydrocarbon isa polyolefin, preferably a polyolefin derived from homopolymerized andinterpolymerized C₂₋₂₈ olefins and mixtures thereof, optionally with atleast one polyene.

In one preferred embodiment, the olefinically unsaturated hydrocarbon isa homopolymer derived from olefins containing from 2 to 4 carbon atoms.Preferably, the polymeric chains have terminal vinylidene groups.

In one embodiment, the polyolefin is an ethylene-alpha-olefin copolymer,preferably an ethylene-propylene copolymer having {overscore (M)}_(n)ranging from about 300 to about 10,000, often to about 5,000 and theethylene content ranges from about 25% to about 75% by weight.

In another preferred embodiment, the polyolefin is a polybutene having{overscore (M)}_(n) ranging from about 300 to about 5,000, often fromabout 600 to about 2,500. Preferably, the polybutene is apolyisobutylene wherein at least about 30 mole %, preferably at leastabout 50 mole % of the polymeric chains have terminal vinylidene groups,and often at least about 70% of the polymeric chains have terminalvinylidene groups. Such materials and methods for preparing them aredescribed in U.S. Pat. Nos. 5,286,823 and 5,408,018, which are expresslyincorporated herein by reference. They are commercially available, forexample under the tradenames ULTRAVIS® (BP Chemicals) and GLISSOPAL®(BASF).

A preferred source of polybutenes is that obtained by polymerization ofa C₄ refinery stream having a butene content of 35 to 75 weight percentand isobutylene content of 15 to 60 weight percent in the presence of aLewis acid catalyst such as aluminum trichloride or boron trifluoride.These polybutenes contain predominantly (greater than 80% of totalrepeating units) isobutylene repeating units of the configuration

These polybutenes are typically monoolefinic, that is they contain butone olefinic bond per molecule.

In one embodiment, the monoolefinic groups arc predominantly vinylidenegroups, e.g., groups of the formula

especially those of the formula

although the polybutenes may also comprise other olefinic configurationsprovided that the polybutene contains at least one allylic H atom.

In another preferred embodiment, the polyolefin is a polypropylene.

In a further embodiment, the polyolefin is a terpolymer derived fromethylene, at least one C₃₋₂₈ olefin and a polyene. Preferably, thepolyene is non-conjugated. In a particularly preferred embodiment, theterpolymer is derived from ethylene, propylene and at least one diene,preferably a non-conjugated diene. Preferably, the terpolymer has{overscore (M)}_(n) ranging from about 1,000 to about 10,000, more oftenfrom about 2500 to about 9,000, and frequently from about 5,000 to about8,000.

In an especially preferred embodiment, the ethylene content of theterpolymer ranges from about 25% to about 85% by weight and thenon-conjugated polyene content ranges from about 0.5% to about 15% byweight. Frequently, the diene comprises at least one cyclic diene, oftenat least one of dicyclopentadiene and an alkylidene norbomene.

The terpolymers are prepared by methods well known to those of skill inthe art and are commercially available, for example those marketed byUniroyal Chemical Co., Inc., Middlebury, Conn., USA, under the tradenameTRILENE®. Specific examples include Trilene 67 and 68, terpolymers ofethylene, propylene and ethylidene norbomene (ENB), and Trilene 55 and65, terpolymers of ethylene, propylene and dicyclopentadiene. Sometypical characteristics of Trilene 67 and 68 are iodine number 19 and 6,ethylene/propylene/(ENB) (wt) 46/54/9.5 and 45/55/3, viscosity averagemolecular weight 7500 and 8000, and average C═C per molecule 5.6 and1.9, respectively.

α,β-Unsaturated Carboxylic Compound

The α,β-unsaturated carboxylic compound used in the preparation of thehydrocarbyl substituted carboxylic compositions of this invention arethemselves prepared by reacting (1) an active methylene compound and (2)a carbonyl compound. They are carboxylic compounds of the generalformulae

wherein each of R^(a), R^(b), R′ and R is defined hereinabove and ingreater detail hereinbelow.

Preferably the α,β-unsaturated carboxylic compound is a polycarboxyliccompound, i.e., at least R′ is OR or R^(b) is C(O)OR.

In one preferred embodiment, the α,β-unsaturated carboxylic compound hasthe general formula (I), R′ is lower alkyl and R^(a) is H and R^(b) is—C(O)R′ wherein R′ is OR and R is lower alyl.

In another preferred embodiment, the carboxylic compound has the generalformula (II), R^(b) is —C(O)OR wherein R is lower alkyl; R^(a) is H; andR′ is R or OR wherein R is H or lower alkyl.

They are often polycarboxylic compounds of the general formula

wherein R^(c) is R;

and each R is, independently, H or hydrocarbyl.

With the reaction of dimethyl malonate and the methyl hemiacetal ofmethyl glyoxylate, a minor amount (ca. 5% yield) of a product having theformula

has been obtained.

Several compounds of this type are described in Hall et al, PolymerBulletin 16, 405-9 (1986); Evans et al, J. Org. Chem. 54 2849 (1989);Hall et al, Macromolecules 8 22, (1975); Stetter et al, Synthesis 626(1981); Wilk, Tetrahedron 53, 7097 (1997); Hawkins et al, U.S. Pat. No.4,049,698 and Roblin et al U.S. Pat. No. 2,293,309.

The α,β-unsaturated carboxylic compound is prepared by reacting (1) anactive methylene compound and (2) a carbonyl compound. The Knoevenagelreaction wherein α,β-unsaturated compounds can be prepared by reactionof active methylene compounds with aldehydes is illustrative. Suchreactions take place with or without solvent and with or withoutcatalyst. Generally, the reaction takes place at temperatures betweenabout 120° C. and 170° for 4 to 8 hours with liberated water beingremoved during reaction. The reaction products are often fractionallydistilled to obtained the desired α,β-unsaturated compound.

Active Methylene Compound

Active methylene compounds (1) used to prepare (B) the α,β-unsaturatedcarboxylic compound have the general formula

wherein each R′ is independently R or OR and each R is, independently, Hor a hydrocarbyl group. Useful active methylene compounds includemalonic acid and esters thereof, especially di-lower alkyl malonateesters, and acetoacetic acid esters, particularly, lower alkyl, such asmethyl, ethyl and propyl acetoacetates.

Especially preferred di-lower alkyl malonate esters are dimethylmalonate, diethyl malonate and methyl ethyl malonate. Especiallypreferred lower alkyl acetoacetates include methyl- orethyl-acetoacetate.

Carbonyl Compound

Carbonyl compounds used to prepare (B) the α,β-unsaturated carboxyliccompound have the general formula

wherein R^(a) is H or hydrocarbyl, especially H or lower alkyl, andR^(b) is a member of the group consisting of H, hydrocarbyl and

wherein each R′ is independently R or OR and each R is, independently, Hor a hydrocarbyl group; and lower alkyl acetals, ketals, hemiacetals andhemiketals of the carbonyl compound.

In one embodiment, the carbonyl compound comprises an aldehyde whereinR^(a) is H and R^(b) is H or lower alkyl. In another embodiment, thecarbonyl compound comprises a ketone wherein each of R^(a) and R^(b) isa lower alkyl group. Formaldehyde is a useful aldehyde. Useful ketonesinclude acetone and methyl ethyl ketone

In a preferred embodiment the carbonyl compound is a compound having thegeneral formula

wherein each R′ is independently R or OR and each R is, independently, Hor a hydrocarbyl group; or a lower alkyl hemiacetal thereof. Preferably,R′ is a group of the formula OR wherein R is independently H or loweralkyl.

Preferred carbonyl compounds are glyoxylic acids and reactiveequivalents thereof. In one preferred embodiment, the carbonyl compoundis glyoxylic acid or the hydrate thereof. Particularly preferred arelower alkyl esters of glyoxylic acid. Especially preferred is a loweralkyl hemiacetals of a lower alkyl glyoxylate, most preferably, themethyl hemiacetal of methyl glyoxylate.

Process for Preparing Hydrocarbyl Group Substituted CarboxylicComposition

This invention is also directed to a process for preparing a hydrocarbylgroup substituted carboxylic composition comprising reacting

(A) an olefinically unsaturated hydrocarbon having at least one allylichydrogen atom, and

(B) an α,β-unsaturated carboxylic compound prepared by reacting

-   -   (1) an active methylene compound of the formula    -    and    -   (2) a carbonyl compound of the general formula    -    wherein R^(a) is H or hydrocarbyl and R^(b) is a member of the        group consisting of H, hydrocarbyl and    -    wherein each R′ is independently R or OR and each R is,        independently, H or a hydrocarbyl group; and lower alkyl        acetals, ketals, hemiacetals and hemiketals of the carbonyl        compound (2). Preferred reactants for use in the process are the        same as those described hereinabove.

Reactants (A) and (B) are generally reacted in amounts ranging fromabout 0.95 to about 4 moles (B) per equivalent of (A), wherein anequivalent of (A) is defined as the molecular weight of (A) divided bythe number of olefinic groups therein. For example, the equivalentweight of a EPDM co-polymer having molecular weight of 10,000 andcontaining 4 olefinic groups is 2,500. In one preferred embodiment,about 3 moles (B) are reacted per equivalent of (A), while in anotherpreferred embodiment, about 1 mole (B) is reacted with one equivalent of(A).

The process may be conducted at ambient pressure, under superatmosphericpressure or under reduced pressure. Usually, except when volatileby-products are being removed from the reaction mixture under reducedpressure, there is no advantage to conduct the reaction under other thanambient pressure.

The process is usually conducted thermally at temperatures ranging fromambient, usually from at least about 20° C. up to about 250° C., moreoften from about 80° C. to about 220° C.

In one embodiment, the process is conducted wherein said reacting of (A)the olefinically unsaturated hydrocarbon having at least one allylichydrogen atom and (B) the α,β-unsaturated carboxylic compound isconducted with the addition of from about 0.1 to about 2.5 moles Cl₂ permole of (B) polycarboxylic compound. In another embodiment, the reactingis conducted with the addition of from about 0.1 to about 2.2 moles Cl₂per equivalent of olefinically unsaturated hydrocarbon. The process withadded chlorine is also generally conducted at an elevated temperature,typically from about 130° C. up to about 200° C.

The following examples illustrate several α,β-unsaturated carboxyliccompounds used in the preparation of the hydrocarbyl substitutedcarboxylic compositions of this invention. In these and in examples thatfollow, unless indicated otherwise, all parts are parts by weight,temperatures are in degrees Celsius, and pressures are atmospheric. Therelationship between parts by weight and parts by volume is as grams tomilliliters. Filtrations are conducted employing a diatomaceous earthfilter aid.

EXAMPLE (B)-1

A reactor is charged with 30 parts dimethyl malonate and 27.2 partsglyoxylic acid methyl ester methyl hemiacetal (hereinafter GMHA). Whilethese are being mixed, 23.17 parts acetic anhydride are added from anaddition funnel at ambient temperature. Heating is begun and after 0.7hour the temperature is 105° C. Heating is continued while distillate iscollected in a Dean-Stark trap. Heating is continued for 4.7 hours whilethe temperature is increased to 130° C. At this point 8 parts by volumedistillate has been collected in the Dean-Stark trap. The temperature isincreased to 160° C. and is maintained for 7.5 hours while collecting8.2 parts by volume additional distillate. Heating at 160° C. iscontinued for 7 hours followed by heating to 200° C. and vacuumdistillation at 10 mm Hg pressure. Two fractions are obtained. Yield ofdesired product is 11.84 parts (25.8%).

EXAMPLE (B)-2

A reactor is charged with 30 parts dimethyl malonate and 27.2 partsGMHA. The materials are heated, under N₂ to 140° C. over 1 hour thentemperature is maintained for 1.5 hours while collecting 6 parts byvolume distillate in Dean-Stark trap The temperature is increased to160° C. and is maintained for 13 hours. The temperature is increased to170° C. and the materials are vacuum stripped at 5.2 mm Hg pressure.Solids and clear colorless liquid distill over and 6.48 parts whitesolid is isolated from the liquid by filtration through filter paper.The solid is the product at 14.13% yield.

EXAMPLE (B)-3

A reactor is charged with 253.73 parts dimethyl malonate and 230.65parts GMHA. The materials me heated, under N₂ to 117° C. then to 125° C.over 5 hours while collecting 50 parts by volume distillate in aDean-Stark trap. The temperature is increased to 130° C. then to 170° C.over 6.5 hours while collecting an additional 36.2 parts distillate. Thetemperature is increased to a maximum of 188° C. at 4.5 mm Hg pressurewhile collecting 199.65 parts distillate (51% yield). The distillate isthe product.

EXAMPLE (B)-4

A reactor is charged with 132.12 parts dimethyl malonate and 120.1 partsGMHA. To the stirring mixture are added 1.79 parts dibutylamine. Thematerials are heated under N₂, to 130° C. over 8.25 hours whilecollecting a total of 36.5 parts by weight distillate in a Dean-Starktrap. The materials are cooled to 110° C. and vacuum distilled. Thefraction collected at 6-10 mm Hg pressure and head temperature 134-152°C. (93.9 parts, 46.4% yield) is the product.

EXAMPLE (B)-5

A reactor is charged with 132.12 parts dimethyl malonate and 120.1 partsGMHA. The materials are heated, under N₂, over 7 hours while collectinga total of 273 parts by volume (235 parts by weight) distillate in aDean-Stark trap. The temperature is increased to 170° C. and thematerials are vacuum distilled. The fraction collected at 156-171° C.pot temperature (21-5 mm Hg pressure, 139-170° C. head temperature)(398.95 parts, 39.5% yield) is the product.

EXAMPLE (B)-6

A reactor is charged with 264.24 parts dimethyl malonate, 240.2 partsGMHA and 5.49 parts 70% aqueous methane sulfonic acid. The materials areheated to 140° C. over 6.25 hours while collecting a total of 63.8 partsdistillate in a Dean-Stark trap. The temperature is increased to 160° C.and is maintained for 2.5 hours while collecting an additional 29 partsby volume distillate. The materials are vacuum distilled collecting230.68 parts, (57.07% yield) at pot temperature 154-162° C., headtemperature 130-140° C. and 5.630 mm Hg pressure as the product.

EXAMPLE (B)-7

A reactor is charged with 132.12 parts dimethyl malonate, 120.01 partsGMHA and 0.89 parts β-alanine. The materials are heated, under N₂, to130° C. while collecting a total of 13.58 parts distillate in aDean-Stark trap. The temperature is increased to 160° C. over 4.5 hoursand is maintained for 2 hours while collecting an additional 11.65 partsdistillate. The materials are vacuum distilled collecting 93.73 parts(46.37% yield) at pot temperature of 134-178° C., head temperature108-120° C. at 4.4-7.5 mm Hg pressure as the product.

EXAMPLE (B)-8

A reactor is charged with 132.12 parts dimethyl malonate, 120.01 partsGMHA and 1.77 parts 30% aqueous NH₄OH. The materials are heated, underN₂, to 151° C. over 3 hours while collecting a total of 30.5 partsdistillate in a Dean-Stark trap. The materials are vacuum distilledcollecting 54.07 parts (26.74% yield) at pot temperature 145-157° C.,head temperature 100-134° C. at 6-7.8 mm Hg pressure as the product.

EXAMPLE (B)-9

A reactor is charged with 532.3 parts GMHA, 585.6 parts dimethylmalonate and 6.08 parts 70% aqueous methanesulfonic acid. The materialsare heated, under N₂, to 130° C. over 5.5 hours while collecting 43.79parts distillate in a Dean-Stark trap. The temperature is increased to140° C. and is maintained for 1 hour while collecting an additional91.82 parts distillate. The temperature is increased to 150° C. over 1hour and is maintained for 5.5 hours while collecting an additional 84.3parts distillate. To the residue are added 4.62 parts Na₂CO₃, thematerials are filtered then vacuum distilled to 150° C. and 10 mm Hgpressure. The fraction distilling at 100-130° C. (246.01 parts, 27.5%yield) is collected as the product.

EXAMPLE (B)-10

A reactor is charged with 720.6 parts GMHA and 660 parts dimethylmalonate. The materials are heated, under N₂, to 120° C. over 6 hours,collecting 81.22 parts distillate in a Dean-Stark trap. The temperatureis increased to 150° C. over 6 hours, collecting an additional 121.93parts distillate. The temperature is maintained for 6 hours, collectingan additional 47.52 parts distillate. The materials are vacuum distilledcollecting 401.69 parts (39.7% yield) at 150-160° C. pot temperature,100-127° C. head temperature at 5 mm Hg pressure as the product.

EXAMPLE (B)-11

A reactor is charged with 160.17 parts dimethyl malonate and 120.1 partsGMHA. The materials are heated under N₂ to 150° C. over 8 hours,collecting a total of 43 parts by volume distillate in a Dean-Starktrap. The temperature is maintained for 4 hours, collecting anadditional 37.8 parts distillate. The materials are vacuum distilled.The fraction distilling 100-120° C. head temperature at 3.3 mm Hgpressure (121.87 parts, 52.9% yield) is collected as product.

EXAMPLE (B)-12

A reactor is charged with 30 parts dimethyl malonate, 27.2 parts GMHAand 0.62 parts 70% aqueous methanesulfonic acid. The materials areheated to 160° C. over 5 hours then the temperature is maintained for 3hours. The materials are vacuum stripped to 130° C. and 4.9 mm Hg. Thesolid-liquid mixture is obtained. The mixture is filtered through paperand 12.85 parts white solids (28% yield) is collected as the product.

EXAMPLE (B)-13

A reactor is charged with 240.2 parts GMHA, 264.24 parts dimethylmalonate and 25 parts of sulfonated poly(styrene-co-divinylbenzene)resin (AMBERLYST®35, Rohm and Haas)). The materials are heated, underN₂, to 120° C. over 7 hours, then maintained at temperature for 13.5hours. The materials are filtered to remove Amnberlyst 35, and theliquid filtrate is vacuum distilled. The fraction distilling at 150° C.pot temperature, 95-125° C. head temperature at 8.3 min Hg pressure(138.1 parts, 34.1% yield), is collected as the product.

EXAMPLE (B)-14

A reactor is charged with 65.07 parts ethyl acetoacetate, 61.02 partsGMHA, 5.0 parts 3-aminopropyl-functionalized silica gel and 100 parts byvolume toluene. The materials are heated, under N₂, to 70° C. over 0.5hour, then temperature is maintained for hours. The temperature isincreased to 80° C. over 3.25 hour then to 90° C. over 2 hours. Thetemperature is maintained at 90° C. for 7 hours. The materials arevacuum distilled. The fraction distilling at 130° C. pot temperature,115° C. head temperature at 5.4 mm Hg pressure (55.3 parts, 54.7% yield,is collected as the product. The product is 93.3% triethylethylenetricarboxylate as determined by gas chromatography/MS.

EXAMPLE (B)-15

A reactor is charged with 300 parts dimethyl malonate and 272.7 partsGMRA. The materials are heated, under N₂, to 123° C. at which time astrong reflux is observed. The materials are heated to 170° C. over 6.5hours while 107.1 parts distillate are collected. The residue, 400.9parts, 87.3% yield is the product

EXAMPLE (B)-16

The crude liquid product (225 parts) of Example (B)-15 is vacuumdistilled at maximum pot temperature of 200° C. and 4 mm Hg pressure.The distillate, a white solid in a clear liquid (total 148.87 parts) iscollected and is the product.

EXAMPLE (B)-17

A reactor is charged with 1322.2 parts dimethyl malonate and 1201.8parts GMHA. The materials are heated, under N₂ to 150° C. over 5 hoursthen temperature is maintained for 5 hours. The temperature is increasedto 145° C., is maintained for 1 hour, then is increased to 150° C. andis maintained at temperature for 4 hours. A total of 427.38 partsdistillate is collected. The materials are vacuum distilled, collectingthe fraction distilling at 130-150° C./5 mm Hg pressure (477.3 parts,23.6% yield).

EXAMPLE (B)-18

A reactor is charged with 260.28 parts ethyl acetoacetate, 240.2 partsGMHA, 20 parts 3-aminopropyl-functionalized silica gel and 400 parts byvolume toluene. The materials are heated, under N₂, to 90° C. over 1hour then temperature is maintained at 90° C. for 7.5 hours whileremoving distillate. The materials are filtered through filter paperwhich is subsequently washed with 100 parts by volume toluene. Thefiltrate and washings are vacuum stripped to 110° C. pot temperature(80° C. head temperature) at 3 mm Hg pressure, yielding 367.51 parts(91.78% yield) as the major product.

EXAMPLE (B)-19

A portion of the product of Example (B)-8 (280 parts) is vacuumdistilled to 135° C. and 4 mm Hg pressure yielding 233.07 partsdistillate as product.

The following examples illustrate hydrocarbyl group substitutedcarboxylic compositions of this invention. Temperatures, pressures, andamounts are as set forth hereinabove.

EXAMPLE 1

A reactor is charged with 555.7 parts of Trilene 67, 555.1 parts mineraloil and 320.9 parts trimethyl ethylenetricarboxylate prepared accordingto the preceding examples. The materials are heated to 170° C., thenover 3 hours, to 200° C. While maintaining temperature, the materialsare heated for 24 hours. The materials are stripped for 5 hours at 160°C. at 2-3.7 mm Hg pressure, collecting 243.36 parts distillate. Theresidue shows 45.8% non-polar material.

EXAMPLE 2

A reactor is charged with 300 parts of polyisobutylene ({overscore(M)}_(n)˜2300, 90% vinylidene, GLISSOPAL® 2300, BASF) and 94 parts ofthe product of Example (B)-11. The materials are heated, under N₂ to170° C. then to 200° C. over 3 hours and held at temperature for 23hours. The materials are vacuum stripped at 200° C. and 4 mm Hg for 2hours. The residue has saponification number (ASTM D-94)=78.04.

EXAMPLE 3

A reactor is charged with 30 parts polyisobutylene (({overscore(M)}_(n)˜1000, containing about 80 mole percent terminal vinylidenegroups, ULTRAVIS® 10 BP Chemicals) and 6.06 parts of the product ofExample (B)-1. The materials are heated, under N₂, to 160° C. over 4hours, then held at temperature for 1.25 hour. The temperature isincreased to 200° C. and is maintained for a total of 19 hours. Thematerials are vacuum stripped to 210° C. at 10 mm Hg for 1 hour. Theresidue has saponification number=119.3. {overscore (M)}_(n)=938 and{overscore (M)}_(w)/{overscore (M)}_(n)=1.94.

EXAMPLE 4

A reactor is charged with 60 parts dimethyl malonate and 54.4 partsGMHA. The materials are heated, under N₂, to 130° C. and are held attemperature for a total of 6 hours, while returning distillate toreactor. The temperature is increased to 140° C. and is maintained for 8hours, collecting 13 parts by volume distillate. The temperature isincreased to 160° C. and is maintained for 7 hours collecting a total of9 parts distillate. To the materials in the reactor are added 60 partsUltravis 10 followed by heating to 180° C. over 2 hours then to 200° C.over 1.5 hours. The materials are held at 200° C. for a total of 10hours, then vacuum stripped at 200° C. and 10 mm Hg for 2 hours. Theresidue has saponification number=89.4, {overscore (M)}_(n)=997 and{overscore (M)}_(w)/{overscore (M)}_(n)=1.92.

EXAMPLE 5

A reactor is charged with 500 parts of polyisobutylene having {overscore(M)}_(n)˜2000 and 101.11 parts of the product of Example (B)-15. Thematerials are heated, under N₂, at 200° C. for 24 hours then vacuumstripped for 2.5 hours at 200° C. and 4 mm Hg pressure. The materialsare filtered using a diatomaceous earth filter aid. Filteredyield=529.52 parts, 96.18%. Filtrate has saponification no=37.23,{overscore (M)}_(n)=1880 and {overscore (M)}_(w)/{overscore(M)}_(n)=3.24.

EXAMPLE 6

A reactor is charged with 500 parts of Glissopal 2300 and 45.83 parts ofthe product of Example (B)-15. The materials are heated, under N₂, to200° C. over 2.5 hour, then temperature is maintained for 13.5 hour. Thematerials are vacuum stripped at 200° C. and 10 mm Hg pressure for 2hours, yielding 526.3 parts (96.43% yield) product.

EXAMPLE 7

A reactor is charged with 500 parts of Glissopal 2300 and 45.83 parts ofthe product of Example (B)-16 The materials are heated, under N₂, to200° C. over 2 hours then the temperature is maintained for 14.5 hours.The materials are stripped for 1.5 hour at 200° C. and 10 mm Hgpressure, yielding 522.29 parts (95.7% yield) product.

EXAMPLE 8

A reactor is charged with 400 parts of Glissopal 2300 and 110 parts ofthe product of Example (B)-3. The materials are heated to 170° C. thenfrom 170° C. to 200° C. over 3 hours. The materials are held at 200° C.for 24 hours then stripped at 200° C. and 4 mm Hg pressure for 2 hours.Residue has saponification number of 89.16, {overscore (M)}_(n)=2078 and{overscore (M)}_(w)/{overscore (M)}_(n)=2.28.

EXAMPLE 9

The procedure of Example 8 is followed replacing Glissopal 2300 with 400parts of a polyisobutylene having {overscore (M)}_(n)˜2000 and using121.33 parts of the product of Example (B)-3. The product hassaponification number=53.57, {overscore (M)}_(n)=1796 and {overscore(M)}_(w)/{overscore (M)}_(n)=3.34.

EXAMPLE 10

The procedure of Example 8 is followed employing 1000 parts Glissopal2300 and 275 parts of the product of Example (B)-5. Stripping is at 210°C. and 2.3 mm Hg pressure for 3 hours. The residue has saponificationnumber=78.55, {overscore (M)}_(n)=2176 and {overscore(M)}_(w)/{overscore (M)}_(n)=2.18.

EXAMPLE 11

A reactor is charged with 400 parts of Glissopal 2300 and 109.9 parts ofthe product of Example (B)-6. The materials are heated, under N₂ over 2hours to 240° C. then are held at temperature for 6 hours. The materialsare vacuum stripped at 220° C. and 4.6 mm Hg for 2 hours. The producthas saponification number=66.9.

EXAMPLE 12

A reactor is charged with 250 parts Glissopal 2300 and 45.33 parts ofthe product of Example (B)-14. The materials are heated, under N₂, to200° C. over 3.6 hour. The temperature is maintained for 3 hours. Thematerials are vacuum stripped to 200° C. at 3.7 mm Hg pressure,collecting 13.4 parts clear pale yellow distillate. The product (272.67parts, ˜100% yield), has saponification no.=48.8, {overscore(M)}_(n)=1922 and {overscore (M)}_(w)/{overscore (M)}_(n)=2.42.

EXAMPLE 13

A reactor is charged with 1700 parts Glissopal 2300 and 467.5 parts ofthe product of Example (B)-17. The materials are heated, under N₂, to200° C. over 3 hours and are maintained at 200° C. for 24 hours, thenvacuum stripped at 200° C. at 2 mm Hg pressure for 1.5 hours. Theresidue has saponification no=85.85.

EXAMPLE 14

A reactor is charged with 164.14 parts Glissopal 2300 and 150.46 partsof the distillate obtained from stripping the reaction mixture ofExample 10. The materials are heated, under N₂, to 200° C. thenmaintained at 200° C. for 24 hours. The materials are allowed to cool toroom temperature, then are heated to 150° C. When stirring is stopped, 2layers form. The bottom layer is removed and the top layer is stipped to200° C. at 8 mm Hg pressure for 2 hours. The residue has saponificationnumber 75.26 and contains 675% non polar materials.

EXAMPLE 15

A reactor is charged with 100 parts of polyisobutylene ({overscore(M)}_(n)=950) and 20 parts of the product of Example (B)-19. Thematerials are heated, under N₂ to 160° C., temperature is maintained for3.5 hours then is increased to 170° C. and is maintained for 22 hours.The temperature is increased to 200° C. and is maintained for 8 hoursfollowed by vacuum stripping to 200° C. and 5 mm Hg pressure. Theresidue is filtered with diatomaceous earth filter aid. Filtratecontains 40% nonpolar material by thin layer chromatography using flameion detector (TLC-FID). Saponification number=63.10.

EXAMPLE 16

A reactor is charged with 100 parts of the polyisobutylene used inExample 15 and 80 parts of the product of Example (B)-19. The materialsare heated, under N₂, to 150° C. then the temperature is maintained for24 hours. When stirring is stopped, an amber colored liquid separatesand settles to the bottom of the flask. The liquid (42.3 parts) isremoved. The remaining materials are heated to 150° C. then stripped to190° C. while collecting 28.7 parts distillate. The residue hassaponification no=46.97 and shows 57% non polar materials by TLC-FID.

EXAMPLE 17

A reactor is charged with 250 parts of polyisobutylene having {overscore(M)}_(n)˜2000 and 75 parts of the product of Example (B)-18. Thematerials are heated over 3 hours, under N₂, to 170° C. then to 200° C.The materials are maintained at temperature for 4 hours then arestripped to 200° C. and 3 mm Hg pressure for 2 hours. The residueseparates into 2 phases.

The hydrocarbyl group substituted carboxylic compositions of thisinvention are useful as additives for lubricating oil compositions andmay be incorporated in a minor amount into a major amount of an oil oflubricating viscosity. They also serve as intermediates to undergofurther reaction with amines, alcohols and metal-containing compounds toprepare derivative compositions which are useful as additives forlubricants and fuels. The carboxylic derivative compositions are alsoincorporated in a minor amount into a major amount of an oil oflubricating viscosity. A major amount is defined herein as any amountgreater than 50% by weight and a minor amount is any amount less than50% by weight provided the total of all components is 100%.

Hydrocarbyl Group Substituted Carboxylic Derivative Compositions

The instant invention is also directed to derivatives of the hydrocarbylsubstituted carboxylic compositions. These derivatives are hydrocarbylgroup substituted carboxylic derivative compositions prepared byreacting at least one hydrocarbyl group substituted carboxyliccomposition of this invention with a reactant selected from the groupconsisting of (a) amines characterized by the presence within theirstructure of at least one condensable H—N<group, (b) alcohols, (c)reactive metal or reactive metal compounds, and (d) a combination of twoor more of any of (a) through (c), the components of (d) being reactedwith the carboxylic composition simultaneously or sequentially, in anyorder.

The hydrocarbyl group substituted carboxylic compositions are describedin detail hereinabove.

Amines

The amines may be monoamines or polyamines, typically polyamines,preferably ethylene amines, amine bottoms or amine condensates. Theamines can be aliphatic, cycloaliphatic, aromatic, or heterocyclic,including aliphatic-substituted cycloaliphatic, aliphatic-substitutedaromatic, aliphatic-substituted heterocyclic, cycloaliphatic-substitutedaliphatic, cycloaliphatic-substituted heterocyclic, aromatic-substitutedaliphatic, aromatic-substituted cycloaliphatic, aromatic-substitutedheterocyclic, heterocyclic-substituted aliphatic,heterocyclic-substituted alicyclic, and beterocyclic-substitutedaromatic amines and may be saturated or unsaturated.

Monoamines useful in this invention generally contain from 1 to about 24carbon atoms, preferably 1 to about 12, and more preferably 1 to about6. Examples of primary monoamines useful in the present inventioninclude methylamine, propylamine, butylamine, cyclopentylamine,dodecylamine, allylamine, cocoamine and stearylamine. Examples ofsecondary monoamines include dimethylamine, dipropylamine,dicyclopentylamine, methylbutylamine, etc.

The monoamine may be an alkanol amine represented by at least one of theformulae:H₂N—R′—OH,and

wherein each R₄ is independently a hydrocarbyl group of one to about 22carbon atoms or hydroxyhydrocarbyl group of two to about 22 carbonatoms, preferably one to about four, and R′ is a divalent hydrocarbylgroup of about two to about 18 carbon atoms, preferably two to aboutfour. The group —R′—OH in such formulae represents thehydroxyhydrocarbyl group. R′ can be an acyclic, alicyclic or aromaticgroup. Typically, R′ is an acyclic straight or branched alkylene groupsuch as an ethylene, 1,2-propylene, 1,2-butylene, 1,2-octadecylene, etc.group. When two R⁴ groups are present in the same molecule they can bejoined by a direct carbon-to carbon bond or through a heteroatom (e.g.,oxygen, nitrogen or sulfur) to form a 5-, 6-, 7- or 8-membered ringstructure. Examples of such heterocyclic amines include N-(hydroxyllower alkyl)-morpholines, -thiomorpholines, -piperidines, -oxazolidines,-thiazolidines and the like. Typically, however, each R⁴ isindependently a methyl, ethyl, propyl, butyl, pentyl or hexyl group.

Examples of alkanolamines include mono- and di- ethanolamine,ethylethanolamine, monomethylethanolamine, etc.

The hydroxyamines can also be ether N-(hydroxyhydrocarbyl) amines. Theseare hydroxy poly(hydrocarbyloxy) analogs of the above-described hydroxyamines (these analogs also include hydroxyl-substituted oxyalkyleneanalogs). Such N-(hydroxyhydrocarbyl) amines can be convenientlyprepared, for example, by reaction of epoxides with aforedescribedamines and can be represented by the formulae:

wherein x is a number from about 2 to about 15 and R₄ and R′ are asdescribed above R₄ may also be a hydrokypoly hydrocarbyloxy) group.

Other useful amines include ether amines of the general formulaR₆OR¹NHR₇wherein R₆ is a hydrocarbyl group, preferably an aliphatic group, morepreferably an alkyl group, containing from 1 to about 24 carbon atoms,R¹ is a divalent hydrocarbyl group, preferably an alkylene group,containing from two to about 18 carbon atoms, more preferably two toabout 4 carbon atoms and R₇ is H or hydrocarbyl, preferably H oraliphatic, more preferably H or alkyl, more preferably H. When R₇ is notH, then it preferably is alkyl containing from one to about 24 carbonatoms. Especially preferred ether amines are those available under thename SURFAM® produced and marketed by Sea Land Chemical Co., Westlake,Ohio.

The amine may also be a polyamine. The polyamine may be aliphatic,cycloaliphatic, heterocyclic or aromatic. Examples of useful polyaminesinclude alkylene polyamines, hydroxy containing polyamines,polyoxyalkylene polyamines, arylpolyamines, and heterocyclic polyamines.

Alkylene polyamines are represented by the formula

wherein n has an average value between about 1 and about 10, preferablyabout 2 to about 7, more preferably about 2 to about 5, and the“Alkylene” group has from 1 to about 10 carbon atoms, preferably about 2to about 6, more preferably about 2 to about 4. R₅ is independentlyhydrogen, an aliphatic group or a hydroxy-substituted oramino-substituted aliphatic group of up to about 30 carbon atoms.Preferably R₅ is H or lower alkyl, most preferably, H.

Alkylene polyamines include methylene-, ethylene-, butylene-,propylene-, pentylene- and other polyamines. Higher homologs and relatedheterocyclic amines such as piperazines and N-amino alkyl-substitutedpiperazines are also included. Specific examples of such polyamines areethylene diamine, diethylene triamine, triethylene tetramine,tris-(2-aminoethyl)amine, propylene diamine,N,N-dimethylaminopropylamine, trimethylene diamine, tripropylenetetramine, tetraethylene pentamine, hexaethylene heptamine,pentaethylenehexamine, aminoethyl piperazine, etc.

Higher homologs obtained by condensing two or more of the above-notedalkylene amines are similarly useful as are mixtures of two or more ofthe aforedescribed polyamines.

Ethylene polyamines, such as some of those mentioned above, arepreferred. They are described in detail under the heading “Dianmines andHigher Amines” in Kirk Othmer's “Encyclopedia of Chemical Technology”,4th Edition, Vol. 8, pages 74-108, John Wiley and Sons, New York (1993)and in Meinhardt, et al, U.S. Pat. No. 4,234,435, both of which arehereby incorporated herein by reference for disclosure of usefulpolyamines. Such polyamines are most conveniently prepared by thereaction of ethylene dichloride with ammonia or by reaction of anethylene imine with a ring opening reagent such as water, ammonia, etc.These reactions result in the production of a complex mixture ofpolyalkylene polyamines including cyclic condensation products such asthe aforedescribed piperazines. Ethylene polyamine mixtures are useful.

Other useful types of polyamine mixtures are those resulting fromstripping of the above-described polyamine mixtures to leave as residuewhat is often termed “polyamine bottoms”. In general, alkylene polyaminebottoms can be characterized as having less than two, usually less than1% (by weight) material boiling below about 200° C. A typical sample ofsuch ethylene polyamine bottoms obtained from the Dow Chemical Companyof Freeport, Tex., designated “E-100” has a specific gravity at 15.6° C.of 1.0168, % nitrogen of 33.15 and a viscosity at 40° C. of 121centistokes. Gas chromatography analysis shows such a sample containsabout 0.93% “Light Ends” (most probably diethylenetriamine), 0.72%triethylenetetramine, 21.74% tetraethylenepentamine and 76.61%pentaethylene hexamine and higher (by weight). These alkylene polyaminebottoms include cyclic condensation products such as piperazine andhigher analogs of diethylenetriamine, triethylenetetramine and the like.

Another useful polyamine is a condensation product obtained by reactionof at least one hydroxy compound with at least one polyamine reactantcontaining at least one primary or secondary amino group. The hydroxycompounds are preferably polyhydric alcohols and amines. Preferably thehydroxy compounds are polyhydric amines. Polyhydric amines include anyof the above-described monoamines reacted with an alkylene oxide (e.g.,ethylene oxide, propylene oxide, butylene oxide, etc.) having two toabout 20 carbon atoms, preferably two to about four. Examples ofpolyhydric amines include tri-(hydroxypropyl)amine,tris-(hydroxymethyl)amino methane, 2-amino-2-methyl-1,3-propanediol,N,N,N′,N′-tetrakis(2-hydroxypropyl) ethylenediamine, andN,N,N′,N′-tetrakis(2-hydroxyethyl) ethylenediamine.

Polyamine reactants, which react with the polyhydric alcohol or amine toform the condensation products or condensed amines, are described above.Preferred polyamine reactants include triethylenetetramine (TETA),tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), andmixtures of polyamines such as the above-described “amine bottoms”.

The condensation reaction of the polyamine reactant with the hydroxycompound is conducted at an elevated temperature, usually about 60° C.to about 265° C. in the presence of an acid catalyst.

The amine condensates and methods of making the same are described inSteckel (U.S. Pat. No. 5,053,152) which is incorporated by reference forits disclosure to the condensates and methods of making aminecondensates.

The polyamines may be hydroxy-containing polyamines. These includehydroxy-containing polyamine analogs of hydroxy monoamines, particularlyalkoxylated alkylenepolyamines. Such polyamines can be made by reactingthe above-described alkylene amines with one or more of theabove-described alkylene oxides.

Specific examples of alkoxylated alkylenepolyamines includeN-(2-hydroxyethyl)ethylenediamine,N,N-di-(2-hydroxyethyl)ethylenediamine, 1-(2-hydroxyethyl)piperazine,mono-(hydroxypropyl)-substituted tetraethylenepentamine,N-(3-hydroxybutyl)-tetramethylene diamine, etc. Higher homologs obtainedby condensation of the above illustrated hydroxy-containing polyaminesthrough amino groups or through hydroxy groups are likewise useful.Condensation through amino groups results in a higher amine accompaniedby removal of ammonia while condensation through the hydroxy groupsresults in products containing ether linkages accompanied by removal ofwater. Mixtures of two or more of any of the aforesaid polyamines arealso useful.

The polyamines may be polyoxyalkylene polyamines, includingpolyoxyethylene and polyoxypropylene diamines and the polyoxypropylenetriamines having average molecular weights ranging from about 200 toabout 2000. Polyoxyalkylene polyamines, includingpolyoxyethylene-polyoxypropylene polyamines, are commercially available,for example under the tradename JEFFAMINES® from Texaco Chemical Co.U.S. Pat. Nos. 3,804,763 and 3,948,800 contain disclosures ofpolyoxyalkylene polyamines and are incorporated herein by reference fortheir disclosure of such materials.

In another embodiment, the polyamine may be a heterocyclic polyamine.The heterocyclic polyamines include aziridines, azetidines, azolidines,tetra- and dihydropyridines, pyrroles, indoles, piperidines, imidazoles,di- and tetrahydroimidazoles, piperazines, isoindoles, purines,N-aminoalkyl-thiomorpholines, N-aminoalkylmorpholines,N-aminoalkyl-piperazines, N,N′-bisaminoalkyl piperazines, azepines,azocines, azonines, azecines and tetra-, di- and perhydro derivatives ofeach of the above and mixtures of two or more of these heterocyclicamines. Preferred heterocyclic amines are the saturated 5- and6-membered heterocyclic amines containing only nitrogen, or nitrogenwith oxygen and/or sulfur in the hetero ring, especially thepiperidines, piperazines, thiomorpholines, morpholines, pyrrolidines,and the like. Piperidine, aminoalkylsubstituted piperidines, piperazine,aminoalkylsubstituted piperazines, morpholine, aminoalkylsubstitutedmorpholines, pyrrolidine, and aminoalkylsubstituted pyrrolidines, areespecially preferred. Usually the aminoa substituents are substituted ona nitrogen atom forming part of the hetero ring. Specific examples ofsuch heterocyclic amines include N-aminopropylmorpholine,N-amino-ethylpiperazine, and N,N′-diaminoethyl-piperazine. Hydroxy alkylsubstituted heterocyclic polyamines are also useful. Examples includeN-hydroxyethylpiperazine and the like.

Hydrazine and substituted-hydrazine can also be used to formnitrogen-containing carboxylic dispersants. At least one of thenitrogens in the hydrazine must contain a hydrogen directly bondedthereto. Preferably there are at least two hydrogens bonded directly tohydrazine nitrogen and, more preferably, both hydrogens are on the samenitrogen. The substituents which may be present on the hydrazine includealkyl, alkenyl, aryl, aralkyl, alkaryl, and the like. Usually, thesubstituents are alkyl, especially lower alkyl, phenyl, and substitutedphenyl such as lower alkoxy-substituted phenyl or loweralkyl-substituted phenyl. Specific examples of substituted hydrazinesare methylhydrazine, N,N-dimethyl-hydrazine, N,N′-dimethylhydrazine,phenylhydrazine, N-phenyl-N′-ethylhydrazine,N-(para-tolyl)-N′-(n-butyl)-hydrazine, N-(para-nitrophenyl)hydrazine,N-(para-nitrophenyl)-N-methyl-hydrazine,N,N′-di(para-chlorophenol)-hydrazine, N-phenyl-N′-cyclohexylhydrazine,amino guanidine bicarbonate, and the like.

The carboxylic derivative compositions produced by reacting thehydrocarbyl group substituted carboxylic composition of the inventionand the amines described above are acylated amines which include aminesalts, amides, imides and imidazolines as well as mixtures thereof. Toprepare the carboxylic derivative compositions from the amines, one ormore of the hydrocarbyl group substituted carboxylic composition and oneor more amines are heated, optionally in the presence of a normallyliquid, substantially inert organic liquid solvent/diluent, attemperatures in the range of from about 80° C. up to the decompositionpoint of any of the reactants or the product, but normally attemperatures in the range of from about 100° C. up to about 300° C.,provided 300° C. does not exceed the decomposition point. Temperaturesof about 125° C. to about 250° C. are normally used. The carboxylic,composition and the amine are reacted in an amount sufficient to providefrom about one-half equivalent up to two moles of amine per equivalentof the carboxylic composition. In another embodiment, the carboxyliccomposition is reacted with from about one-half equivalent up to onemole of amine per equivalent of the carboxylic composition. For thepurpose of this invention, an equivalent of amine is that amount ofamine corresponding to the total weight of amine divided by the totalnumber of nitrogens present having at least one H—N<group. Thus, octylamine has an equivalent weight equal to its molecular weight;ethylenediamine has an equivalent weight equal to one-half its molecularweight, and aminoethylpiperazine, with 3 nitrogen atoms but only twohaving at least one H—N<group, has an equivalent weight equal toone-half of its molecular weight.

Alcohols

The carboxylic compositions may be reacted with (b) alcohols. Alcoholsuseful as (b) in preparing carboxylic derivative compositions of thisinvention from the hydrocarbyl group substituted carboxylic compositionpreviously described include those compounds of the general formulaR₃—(OH)_(m)wherein R₃ is a monovalent or polyvalent organic radical joined to the—OH groups through carbon-to-oxygen bonds (that is,—C—OHwherein the carbon is not part of a carbonyl group) and m is an integerof from 1 to about 10, usually 2 to about 6. As with the amine reactant(a), the alcohols can be aliphatic, cycloaliphatic, aromatic, andheterocyclic, including aliphatic-substituted cycloaliphatic alcohols,aliphatic-substituted aromatic alcohols, aliphatic-substitutedheterocyclic alcohols, cycloaliphatic-substituted aliphatic alcohols,cycloaliphatic-substituted aromatic alcohols, cycloaliphatic-substitutedheterocyclic alcohols, heterocyclic-substituted aliphatic alcohols,heterocyclic-substituted cycloaliphatic alcohols, andheterocyclic-substituted aromatic alcohols. Except for polyoxyalkylenealcohols, the mono- and polyhydric alcohols corresponding to the aboveformula will usually contain not more than about 40 carbon atoms andgenerally not more than about 20 carbon atoms. The alcohols may containnon-hydrocarbon substituents of the same type mentioned with respect tothe amines above, that is, non-hydrocarbon substituents which do notinterfere with the reaction of the alcohols with the acylating reagentsof this invention. In general, polyhydric alcohols are preferred.

The monohydric and polyhydric alcohols useful as (b) include monohydroxyand polyhydroxy aromatic compounds. Monohydric and polyhydric phenolsand naphthols are preferred hydroxyaromatic compounds. Thesehydroxy-substituted aromatic compounds may contain other substituents inaddition to the hydroxy substituents such as halo, alkyl, alkenyl,alkoxy, alkyl-mercapto, nitro and the like. Usually, the hydroxyaromatic compound will contain 1 to 4 hydroxy groups. The aromatichydroxy compounds are illustrated by the following specific examples:phenol, beta-naphthol, cresols, resorcinol, catechol, carvacrol, thymol,eugenol, p,p′-dihydroxybiphenyl, hydroquinone, pyrogallol,phloroglucinol, orcin, guaicol, 2,4-dibutylphenol,propenetetramer-substituted phenol, didodecylphenol,4,4′-methylene-bis-methylene-bis-phenol, alphadecyl-beta-naphthol,polyisobutenyl-(molecular weight of about 1000)-substituted phenol, thecondensation product of heptylphenol with 0.5 mole of formaldehyde, thecondensation product of octylphenol with acetone,di(hydroxyphenyl)oxide, di(hydroxyphenyl)sulfide,di(hydroxyphenyl)disulfide, and 4-cyclohexylphenol. Phenol itself andaliphatic hydrocarbon-substituted phenols, e.g., alkylated phenolshaving up to 3 aliphatic hydrocarbon substituents are especiallypreferred. Each of the aliphatic hydrocarbon substituents may contain100 or more carbon atoms but usually will have from 1 to 20 carbonatoms. Alkyl and alkenyl groups are the preferred aliphatic hydrocarbonsubstituents.

Further specific examples of monohydric alcohols which can be used as(b) include monohydric alcohols such as methanol, ethanol, isooctanol,cyclohexanol, behenyl alcohol, neopentyl alcohol, isobutyl alcohol,benzyl alcohol, beta-phenethyl alcohol, 2,-methylcyclohexanol,monomethyl ether of ethylene glycol, monobutyl ether of ethylene glycol,monopropyl ether of diethylene glycol, monododecyl ether of triethyleneglycol, monooleate of ethylene glycol, monostearate of diethyleneglycol, sec-pentyl alcohol, tert-butyl alcohol, and dioleate ofglycerol. Alcohols within (b) may be unsaturated alcohols such as allylalcohol, cinnamyl alcohol, 1-cyclohexene-3-ol and oleyl alcohol.

Other specific examples of alcohols useful as (b) are the ether alcoholsand amino alcohols including, for example, the oxyalkylene,oxy-arylene-, aminoalkylene-, and aminoarylene-substituted alcoholshaving one or more oxyalkylene, aminoalkylene oramino-aryleneoxy-arylene groups. They are exemplified by CELLOSOLVE®,CARBITOL®, phenoxyethanol, heptylphenyl-(oxypropylene)₆-OH,octyl-(oxyethylene)₃₀-OH phenyl-(oxyoctylene)₂-OH,mono-(heptylphenyl-oxypropylene)substituted glycerol, poly(styreneoxide), aminoethanol, 3-aminoethylpentanol, di(hydroxyethyl)amine,p-aminophenol, tri(hydroxypropyl)amine, N-hydroxyethyl ethylenediamine,N,N,N′,N′-tetrahydroxy-trimethylenediamine, and the like. The polyhydricalcohols preferably contain from 2 to about 10 hydroxy groups. They areillustrated, for example, by the alkylene glycols and polyoxyalkyleneglycols mentioned above such as ethylene glycol, triethylene glycol,tetraethylene glycol, dipropylene glycol, dibutylene glycol, and otheralkylene glycols and polyoxyalkylene glycols in which the alkylenegroups contain 2 to about 8 carbon atoms.

Other useful polyhydric alcohols include glycerol, monooleate ofglycerol, monostearate of glycerol, monomethyl ether of glycerol,pentaerythritol, n-butyl ester of 9,10-dihydroxy stearic acid, methylester of 9,10-dihydroxy stearic acid, 1,2-butanediol, 2,3-hexanediol,2,4-hexanediol, pinacol, erythritol, arabitol, sorbitol, mannitol,1,2-cyclohexanediol, and xylene glycol. Carbohydrates such as sugars,starches, celluloses, and so forth likewise can be used as (b). Thecarbohydrates may be exemplified by glucose, fructose, sucrose,rhamnose, mannose, glyceraldehyde, and galactose.

Polyhydric alcohols having at least 3 hydroxyl groups, some, but not allof which have been esterified with an aliphatic monocarboxylic acidhaving from about 8 to about 30 carbon atoms such as octanoic acid,oleic acid, stearic acid, linoleic acid, dodecanoic acid or tall oilacid are useful as (b). Further specific examples of such partiallyesterified polyhydric alcohols are the monooleate of sorbitol,distearate of sorbitol, monooleate of glycerol, monostearate ofglycerol, didodecanoate of erythritol, and the like.

A preferred class of alcohols suitable as (b) are those polyhydricalcohols containing up to about 12 carbon atoms, and especially thosecontaining 3 to 10 carbon atoms. This class of alcohols includesglycerol, erythritol, pentaerythritol, dipentaerythritol, gluconic acid,glyceraldehyde, glucose, arabinose, heptanediols, hexanetriols,butanetriols, guinic acid, 2,2,6,6-tetrakis(hydroxymethyl)cyclohexanol,1,10-decanediol, digitalose, and the like. Aliphatic alcohols containingat least three hydroxyl groups and up to 10 carbon atoms areparticularly preferred.

An especially preferred class of polyhydric alcohols for use as (b) arethe polybydric alkanols containing 3 to 10 carbon atoms andparticularly, those containing 3 to 6 carbon atoms and having at leastthree hydroxyl groups. Such alcohols are exemplified by glycerol,erythritol, pentaerythritol, mannitol, sorbitol, 2-hydroxymethyl-2-methyl-1,3-propanediol(trimethylolethane),2-hydroxy-methyl-2-ethyl-1,3-propanediol(trimethylpropane),1,2,4-hexanetriol, and the like.

From what has been stated above, it is seen that (a) may containalcoholic hydroxy substituents and (b) can contain primary, secondary,or tertiary amino substituents. Thus, amino alcohols can fall into both(a) and (b) provided they contain at least one primary or secondaryamino group. If only tertiary amino groups are present, the aminoalcohol belong only in (b).

Reactive Metals

Reactive metals or reactive metal compounds useful as (c) are thosewhich will form carboxylic acid metal salts with the hydrocarbyl groupsubstituted carboxylic composition of this invention and those whichwill form metal-containing complexes with the carboxylic derivativecompositions produced by reacting the hydrocarbyl group substitutedcarboxylic composition with amines and/or alcohols as discussed above.

Reactive metal compounds useful for preparing metal salts of hydrocarbylgroup substituted carboxylic composition of this invention include thosesalts containing metals selected from the group consisting of Group Imetals, Group II metals, Al, Pb, Sn, Co and Ni. Examples of compoundsinclude the oxides, hydroxides, alcoholates, and carbonates of Li, Na,K, Ca, Ba, Pb, Al, Sn, Ni and others. While reactive metals may also beemployed, it is generally more convenient, and often more economical toemploy the metal salts as reactants. An extensive listing of reactivemetal compounds useful for preparing the metal salts of the hydrocarbylgroup substituted carboxylic composition is provided in U.S. Pat. No.3,271,310 (LeSuer) which is expressly incorporated herein by reference.

Reactive metal compounds useful as (c) for the formation of complexeswith the reaction products of the acylating reagents of this inventionand amines are disclosed in U.S. Pat. No. 3,306,908. Complex-formingmetal reactants useful as (c) include the nitrates, nitrites, halides,carboxylates, phosphates, phosphites, sulfates, sulfites, carbonates,borates, and oxides of cadmium as well as metals having atomic numbersfrom 24 to 30 (including chromium, manganese, iron, cobalt, nickel,copper and zinc). These metals are the so-called transition orcoordination metals, i.e., they are capable of forming complexes bymeans of their secondary or coordination valence. Specific examples ofthe complex-forming metal compounds useful as the reactant in thisinvention are cobalt, cobaltous oxide, cobaltous chloride, cobalticchloride, chromous acetate, chromic acetate, chromic sulfate, chromichexanoate, manganous acetate, manganous benzoate, manganous nitrate,ferrous acetate, ferric benzoate, ferrous bromide, nickel nitrate,nickel dioleate, nickel stearate, cupric benzoate, cupric formate,cupric nitrite; zinc benzoate, zinc borate, zinc chromate, cadmiumbenzoate, cadmium carbonate, cadmium butyrate. Hydrates of the abovecompounds are especially convenient for use in the process of thisinvention.

U.S. Pat. No. 3,306,908 is expressly incorporated herein by referencefor its discussion of reactive metal compounds suitable for forming suchcomplexes and its disclosure of processes for preparing the complexes.Basically, those processes are applicable to the carboxylic derivativecompositions of the acylating reagents of this invention with the aminesas described above by substituting, or on an equivalent basis, theacylating reagents of this invention with the high molecular weightcarboxylic acid acylating agents disclosed in U.S. Pat. No. 3,306,908.The ratio of equivalents of the acylated amine thus produced and thecomplex-forming metal reactant remains the same as disclosed in U.S.Pat. No. 3,306,908.

The following examples illustrate carboxylic derivative compositions ofthis invention. Temperatures, pressures, and amounts are as set forthhereinabove. Filtrations employ a diatomaceous earth filter aid.

EXAMPLE A

A reactor is charged with 300 parts of the product of Example 8 and 250parts mineral oil. The materials are heated, under N₂, to 110° C.whereupon 18.98 parts of an ethylene polyamine mixture having anequivalent weight of 39.78 are added over 0.2 hour. The materials areheated to 160° C. over 1.25 hour and are maintained at temperature for13 hours while removing 3 parts by volume distillate. The materials arefiltered at 120° C. The reactor is rinsed with 53.68 parts mineral oiland the rinsings are filtered and combined with the first filtrate. Thefiltrate contains 0.989% N, has saponification number=19.53 and totalbase number=15.06.

EXAMPLE B

A reactor is charged with 300 parts of the product of Example 10 and305.75 parts of mineral oil. The materials are heated, under N₂, to 110°C. whereupon 19.19 parts of an ethylene polyamine bottoms containing31.5% N (HPA-X, Union Carbide) are added over 0.2 hour. The materialsare heated to 170° C. over 3 hours and maintained at temperature for8.25 hour. The materials are filtered with a diatomaceous earth filteraid at 130° C. The filtrate contains 0.995% N, saponificationnumber=20.29 and total base number=18.59.

EXAMPLE C

The procedure of Example B is repeated with 300 parts of the product ofExample 10, 24.41 parts HPA-X polyamine bottoms and 310.97 parts mineraloil. The filtrate contains 1.185% N, saponification number=10.56 andtotal base number=23.5.

EXAMPLE D

A reactor is charged with 1791 parts of the product of Example 13,1819.58 parts mineral oil and 116.26 parts HPA-X polyamine bottoms. Thematerials are heated, Under N₂, to 170° C. over 3 hours then maintainedat 170° C. for a total of 13.5 hours while collecting a total of 50.27parts distillate. The materials are filtered at 110° C. with adiatomaceous earth filter aid. The filtrate contains 1.03% N, and totalbase number=16.53.

EXAMPLE E

A reactor is charged with 200 parts of the product of Example 12, 7.38parts HPA-X polyamine bottoms and 701.91 parts mineral oil. Thematerials are heated to 100° C. over 0.25 hour, then the temperature isincreased to 170° C., is maintained at temperature for 1.5 hours, thentemperature is increased to 180° C., is maintained for 0.5 hour, thentemperature is increased to 190° C. and is maintained for 5 hours. Thematerials are cooled to 130° C., mixed with 17.1 parts diatomaceousearth filter aid then filtered through cloth. Filtrate has %N=0.55,Total Base No=10.52.

EXAMPLE F

A reactor is charged with 371.3 parts of the product of Example 10, 119parts pentaerythritol and 300 parts mineral oil. To the stirred mixtureare added 2 parts 70% aqueous methanesulfonic acid. The materials areheated to 210° C. and the temperature is maintained for 3 hours whileremoving distillate as it forms. The materials are then filtered at 100°C.

EXAMPLE G

A reactor is charged with 300 parts of the product of Example F and 4.5parts of HPA-X polyamines bottoms. The materials are heated at 145° C.for 2 hours then collected.

EXAMPLE H

A reactor is charged with 142 parts of the product of Example 10, 60parts mineral oil, 10 parts water and 4 parts zinc oxide. The materialsare mixed and heated at 160° C. for 5 hours, vacuum stripped andfiltered.

EXAMPLE I

A mixture of 100 parts of the product of Example H and 2 parts of EPA-Xpolyamines bottoms is mixed and heated at 150° C. for 2 hours, thencollected.

The Oil of Lubricating Viscosity

The lubricating compositions of this invention employ an oil oflubricating viscosity, including natural or synthetic lubricating oilsand mixtures thereof.

Natural oils include animal oils and vegetable oils (e.g. castor oil,lard oil) as well as mineral lubricating oils such as liquid petroleumoils and solvent-treated or acid treated mineral lubricating oils of theparaffinic, naphthenic or mixed paraffinic-naphthenic types. Oils oflubricating viscosity derived from coal or shale are also useful.Synthetic lubricating oils include hydrocarbon oils and halosubstitutedhydrocarbon oils such as polymerized and interpolymerized olefins, etc.and mixtures thereof, alkylbenzenes, polyphenyl, (e.g., biphenyls,terphenyls, alkylated polyphenyls, etc.), alkylated diphenyl ethers andalkylated diphenyl sulfides and the derivatives, analogs and homologuesthereof and the like.

Alkylene oxide polymers and interpolymers and derivatives thereof wheretheir terminal hydroxyl groups have been modified by esterification,etherification, etc., constitute another useful class of known syntheticlubricating oils.

Another suitable class of synthetic lubricating oils that can be usedcomprises the esters of di- and polycarboxylic acids and those made fromC₅ to C₂₀ monocarboxylic acids and polyols and polyolethers.

Other synthetic lubricating oils include liquid esters ofphosphorus-containing acids, polymeric tetrahydrofurans and the like,silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, orpolyaryloxy-siloxane oils and silicate oils.

Unrefined, refined and redefined oils, either natural or synthetic (aswell as mixtures of two or more of any of these) of the type disclosedhereinabove can be used in the compositions of the present invention.Unrefined oils are those obtained directly from natural or syntheticsources without further purification treatment. Refined oils are similarto the unrefined oils except they have been further treated in one ormore purification steps to improve one or more properties. Refined oilsinclude solvent refined oils, hydrorefined oils, hydrofinished oils,hydrotreated oils, and oils obtained by hydrocracking andhydroisomerization techniques.

Rerefined oils are obtained by processes similar to those used to obtainrefined oils applied to refined oils which have been already used inservice. Such rerefined oils often are additionally processed bytechniques directed to removal of spent additives and oil breakdownproducts.

Specific examples of the above-described oils of lubricating viscosityare given in Chamberlin, III, U.S. Pat. No. 4,326,972, European PatentPublication 107,282, and A. Sequeria, Jr., Lubricant Base Oil and WaxProcessing, Chapter 6, Marcel Decker, Inc., New York (1994), each ofwhich is hereby incorporated by reference for relevant disclosurescontained therein.

A basic, brief description of lubricant base oils appears in an articleby D. V. Brock, “Lubrication Engineering”, Volume 43, pages 184-5,March, 1987, which article is expressly incorporated herein by referencefor relevant disclosures contained therein.

The Normally Liquid Fuels

As indicated hereinabove, the products of this invention may also beused as additives for normally liquid fuels.

The fuels used in the fuel compositions of this invention are well knownto those skilled in the art and usually contain a major portion of anormally liquid fuel such as hydrocarbonaceous petroleum distillate fuel(e.g., motor gasoline as defined by ASTM Specifications D-439-89 andD-4814-91 and diesel fuel or fuel oil as defined in ASTM SpecificationsD-396-90 and D-975-91). Fuels containing non-hydrocarbonaceous materialssuch a alcohols, ether, organo-nitro compounds and the like, are alsowithin the scope of this invention as are liquid fuels derived fromvegetable or mineral sources. A range of alcohol and ether typecompounds are described as oxygenates. Oxygenate-containing fuels aredescribed in ASTM D-4814-91. Mixtures of any of the above-describedfuels are useful.

Particularly preferred fuels are gasoline, that is, a mixture ofhydrocarbons having an ASTM boiling point of 60° C. at the 10%distillation point to about 205° C. at the 90% distillation point,oxygenates, and gasoline-oxygenate blends, all as defined in theaforementioned ASTM Specifications for automotive gasolines. Mostpreferred is gasoline.

The fuel compositions typically contain from about 0.001% to about 2% byweight, more often up to about 0.5%, even more often up to about 0.2% byweight of the additives of this invention.

The fuel compositions of the present invention may contain otheradditives which are well known to those skilled in the art. These caninclude anti-knock agents such as tetra-alkyl lead compounds, leadscavengers such as halo-alkanes, dyes, antioxidants such as hinderedphenols, rust inhibitors such as alkylated succinic acids and anhydridesand derivatives thereof, bacteriostatic agents, auxiliary dispersantsand detergents, gum inhibitors, fluidizers, metal deactivators,demulsifiers, anti-icing agents and the like. The fuel compositions ofthis invention may be lead-containing or lead-free fuels. Preferred arelead-free fuels.

Other Additives

As mentioned, lubricating oil compositions of this invention may containother components. The use of such additives is optional and the presencethereof in the compositions of this invention will depend on theparticular use and level of performance required. Thus the otheradditive may be included or excluded. The compositions may comprise azinc salt of a dithiophosphoric acid. Zinc salts of dithiophosphoricacids are often referred to as zinc dithiophosphates, zincO,O′-dihydrocarbyl dithiophosphates, and other commonly used names. Theyare sometimes referred to by the abbreviation ZDP. One or more zincsalts of dithiophosphoric acids may be present in a minor amount toprovide additional extreme pressure, anti-wear and anti-oxidancyperformance.

In addition to zinc salts of dithiophosphoric acids discussedhereinabove, other additives that may optionally be used in thelubricating oils of this invention include, for example, auxiliarydetergents and dispersants, viscosity improvers, oxidation inhibitingagents, pour point depressing agents, extreme pressure agents, anti-wearagents, color stabilizers and anti-foam agents. The above-mentioneddispersants and viscosity improvers may be used in addition to thecompositions of this invention.

Auxiliary extreme pressure agents and corrosion and oxidation inhibitingagents which may be included in the compositions of the invention areexemplified by chlorinated aliphatic hydrocarbons, organic sulfides andpolysulfides, phosphorus esters including dihydrocarbon andtrihydrocarbon phosphites, molybdenum compounds, and the like.

Auxiliary viscosity improvers (also sometimes referred to as viscosityindex improvers or viscosity modifiers) may be included in thecompositions of this invention. Viscosity improvers are usuallypolymers, including polyisobutenes, polymethacrylic acid esters, dienepolymers, polyalkyl styrenes, esterified styrene-maleic anhydridecopolymers, alkenylarene-conjugated diene copolymers and polyolefins.Multifunctional viscosity improvers, other than those of the presentinvention, which also have dispersant and/or antioxidancy properties areknown and may optionally be used in addition to the products of thisinvention. Such products are described in numerous publicationsincluding those mentioned in the Background of the Invention. Each ofthese publications is hereby expressly incorporated by reference.

Pour point depressants are often included in the lubricating oilsdescribed herein. See for example, page 8 of “Lubricant Additives” by C.V. Smalheer and R. Kennedy Smith (Lezius-Hiles Company Publisher,Cleveland, Ohio, 1967). Pour point depressants, techniques for theirpreparation and their use are described in U.S. Pat. Nos. 2,387,501;2,015,748; 2,655,479; 1,815,022; 2,191,498; 2,666,748; 2,721,877;2,721,878; and 3,250,715 which are expressly incorporated by referencefor their relevant disclosures.

Anti-foam agents used to reduce or prevent the formation of stable foaminclude silicones or organic polymers. Examples of these and additionalanti-foam compositions are described in “Foam Control Agents”, by HenryT. Kerner (Noyes Data Corporation, 1976), pages 125-162.

Detergents and dispersants may be of the ash-producing or ashless type.The ash-producing detergents are exemplified by oil soluble neutral andbasic salts of alkali or alkaline earth metals with sulfonic acids;carboxylic acids, phenols or organic phosphorus acids characterized by aleast one direct carbon-to-phosphorus linkage.

The term “basic salt” is used to designate metal salts wherein the metalis present in stoichiometrically larger amounts than the organic acidradical. Basic salts and techniques for preparing and using them arewell known to those skilled in the art and need not be discussed indetail here.

Ashless detergents and dispersants are so-called despite the fact that,depending on its constitution, the detergent or dispersant may uponcombustion yield a nonvolatile residue such as boric oxide or phosphoruspentoxide; however, it does not ordinarily contain metal and thereforedoes not yield a metal-containing ash on combustion. Many types areknown in the art, and are suitable for use in the lubricants of thisinvention. The following are illustrative:

(1) Reaction products of carboxylic acids (or derivatives thereof)containing at least about 34 and preferably at least about 54 carbonatoms with nitrogen containing compounds such as amine, organic hydroxycompounds such as phenols and alcohols, and/or basic inorganicmaterials. Examples of these “carboxylic dispersants” are described inBritish Patent number 1,306,529 and in many U.S. patents including thefollowing:

3,163,603 3,381,022 3,542,680 3,184,474 3,399,141 3,567,637 3,215,7073,415,750 3,574,101 3,219,666 3,433,744 3,576,743 3,271,310 3,444,1703,630,904 3,272,746 3,448,048 3,632,510 3,281,357 3,448,049 3,632,5113,306,908 3,451,933 3,697,428 3,311,558 3,454,607 3,725,441 3,316,1773,467,668 4,194,886 3,340,281 3,501,405 4,234,435 3,341,542 3,522,1794,491,527 3,346,493 3,541,012 5,696,060 3,351,552 3,541,678 5,696,067 RE26,433

(2) Reaction products of relatively high molecular weight aliphatic oralicyclic halides with amines, preferably polyalkylene polyamines. Thesemay be characterized as “amine dispersants” and examples thereof aredescribed for example, in the following U.S. patents:

3,275,554 3,454,555 3,438,757 3,565,804

(3) Reaction products of alkyl phenols in which the alkyl groupscontains at least about 30 carbon atoms with aldehydes (especiallyformaldehyde) and amines (especially polyalkylene polyamines), which maybe characterized as “Mannich dispersants”. The materials described inthe following U.S. patents are illustrative:

3,413,347 3,725,480 3,697,574 3,726,882 3,725,277

(4) Products obtained by post-treating the carboxylic amine or Mannichdispersants with such reagents as urea, thiourea, carbon disulfide,aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinicanhydrides, nitriles, epoxides, boron compounds, phosphorus compounds orthe like. Exemplary materials of this kind are described in thefollowing U.S. patents:

3,036,003 3,282,955 3,493,520 3,639,242 3,087,936 3,312,619 3,502,6773,649,229 3,200,107 3,366,569 3,513,093 3,649,659 3,216,936 3,367,9433,533,945 3,658,836 3,254,025 3,373,111 3,539,633 3,697,574 3,256,1853,403,102 3,573,010 3,702,757 3,278,550 3,442,808 3,579,450 3,703,5363,280,234 3,455,831 3,591,598 3,704,308 3,281,428 3,455,832 3,600,3723,708,522 4,234,435

(5) Polymers and copolymers of oil-solubilizing monomers such as decylmethacrylate, vinyl decyl ether and high molecular weight olefins withmonomers containing polar substituents, e.g., aminoalkyl acrylates ormethacrylates, acrylamides and poly-(oxyethylene)-substituted acrylates.These may be characterized as “polymeric dispersants” and examplesthereof are disclosed in the following U.S. patents:

3,329,658 3,666,730 3,449,250 3,687,849 3,519,565 3,702,300The above-noted patents are incorporated by reference herein for theirdisclosures of ashless dispersants.

The above-illustrated additives may each be present in lubricatingcompositions at a concentration of as little as 0.001% by weight,usually ranging from about 0.01% to about 20% by weight. In mostinstances, they each contribute from about 0.1% to about 10% by weight,more often up to about 5% by weight.

Additive Concentrates

The various compositions and other additives described herein can beadded directly to the lubricant. Preferably, however, they are dilutedwith a substantially inert, normally liquid organic diluent such asmineral oil, naphtha, benzene, toluene or xylene, to form an additiveconcentrate. Preferred additive concentrates contain the diluentsreferred to hereinabove. These concentrates usually comprise about 0.1to about 80% by weight of the compositions of this invention and maycontain, in addition, one or more other additives known in the art ordescribed hereinabove. Concentrations such as 15%, 20%, 30% or 50% orhigher may be employed.

The following Examples illustrate several additive concentratescomprising compositions of this invention. All parts are parts by weightand, except for products of examples recited herein, amounts are on anoil or other diluent free basis.

Concentrates I-II

Each of the below listed additive concentrates is prepared by combining7.61 parts of Zn mixed isopropyl-methyl amyl phosphorodithioate, 2.7parts C₁₂₋₁₈ alkyl sulfide, 5.5 parts alkylated diphenyl amine, 1 partof sodium overbased (MR 16) polyisobutylene (M_(n)˜1000) substitutedsuccinic acid, 2 parts calcium overbased (MR 11) alkyl benzene sulfonicacid, 1.54 parts magnesium overbased (MR 14.7) alkyl benzene sulfonicacid, 2.8 parts calcium overbased (MR 3.5) sulfurized alkyl phenol, 0.09parts of a kerosene solution of a commercial silicone antifoam, 49.1part of the indicated product of this invention and sufficient mineraloil to bring the total weight of the additive concentrate to 100 parts.

Concentrate I II Product of Example: A DConcentrate III

An additive concentrate is prepared by combining 9.2 partspolyisobutylene (M_(n)˜1000) substituted succinic anhydride-ethylenepolyamine reaction product, 5.8 parts of Zn mixed isopropyl-methyl amylphosphorodithioate, 4 parts sulfurized butadiene-butyl acrylateDiels-Alder adduct, 0.5 parts alkylated diphenyl amine, 4.0 partscalcium overbased (MR 11) alkyl benzene sulfonic acid, 1.7 partsmagnesium overbased (MR 14.7) alkyl benzene sulfonic acid, 64 partscalcium overbased (MR 3.5) sulfurized alkyl phenol, 0.62 parts calciumoverbased (MR 2.8) alkyl benzene sulfonic acid, 2.08 parts2,6-di-t-butyl-4-dodecyl phenol, 0.09 parts of a kerosene solution of acommercial silicone antifoam, 38.1 parts of the product of Example A andsufficient mineral oil to bring the total weight of the additiveconcentrate to 100 parts.

Concentrates IV and V

Each of the below listed additive concentrates is prepared by combining4.5 parts alkylated diphenyl amine, 6.5 parts Zn mixed isopropyl-methylamyl phosphorodithioate, 6.2 parts calcium overbased (MR 2.8) sulfurizedalkyl phenol, 0.9 parts calcium overbased (MR 11) alkyl benzene snlfonicacid, 11.2 parts calcium overbased (MR 2.8) alkyl benzene sulfonic acid,54.3 parts of the indicated product of this invention and sufficientmineral oil to bring the total weight of the additive concentrate to 100parts.

Concentrate IV V Product of Example: B CLubricating Oil Compositions

The instant invention also relates to lubricating oil compositionscontaining the carboxylic compositions of the invention. As notedhereinabove, the carboxylic compositions of this invention may beblended directly into an oil or lubricating viscosity or, more often,are incorporated into an additive concentrate containing one or moreother additives which in turn is blended into the oil.

Lubricant Examples AA-BB

SAE 5W-30 lubricating oil compositions are prepared by blending 8.5parts of a 9% in mineral oil solution of anethylene-propylene-dicyclopentadiene copolymer viscosity improver, 0.2parts of a 46% in oil solution of an amine neutralized styrene-maleatecopolymer, and 11 parts of the indicated additive concentrate insufficient mineral oil (Exxon stocks) to make 100 parts of lubricatingoil composition.

Lubricant AA BB Product of Example: Concentrate I Concentrate IILubricant Examples CC-DD

SAE 15W-40 lubricating oil compositions are prepared by blending 8.5parts of a 9.5% in oil solution of an ethylene propylene copolymerviscosity improver, 0.12% of a 53% in oil solution of a polymethacrylateviscosity improver, and 13.2 parts of the indicated additive concentratein sufficient mineral oil (Exxon stocks) to make 100 parts oflubricating oil composition.

Lubricant CC DD Product of Example: Concentrate IV Concentrate VLubricant Example EE

An SAE 10W40 lubricating oil composition is prepared by blending 10.5parts of a 12.5% in oil solution of an ethylene-propylene copolymer,0.12% of a 53% in oil solution of a polymethacrylate viscosity improver,and 14.4 parts of Additive Concentrate III into sufficient mineral oil(Esso 145N) to make 100 parts of lubricating oil composition.

It is known that some of the materials described above may interact inthe final formulation, so that the components of the final formulationmay be different from those that are initially added. For instance,metal ions (of, e.g., a detergent) can migrate to other acidic sites ofother molecules. The products formed thereby, including the productsformed upon employing the composition of the present invention in itsintended use, may not susceptible of easy description. Nevertheless, allsuch modifications and reaction products are included within the scopeof the present invention; the present invention encompasses thecomposition prepared by admixing the components described above.

Each of the documents referred to above is incorporated herein byreference. Except in the examples, or where otherwise explicitlyindicated, all numerical quantities in this description specifyingamounts of materials, reaction conditions, molecular weights, number ofcarbon atoms, and the like, are to be understood as modified by the word“about”. Unless otherwise indicated, each chemical or compositionreferred to herein should be interpreted as being a commercial gradematerial which may contain the isomers, by-products, derivatives, andother such materials which are normally understood to be present in thecommercial grade. However, the amount of each chemical component ispresented exclusive of any solvent or diluent oil which may becustomarily present in the commercial material, unless otherwiseindicated. It is to be understood that the upper and lower amount,range, and ratio limits set forth herein may be independently combined.As used herein, the expression “consisting essentially of” permits theinclusion of substances which do not materially affect the basic andnovel characteristics of the composition under consideration.

While the invention has been explained in relation to its preferredembodiments, it is to be understood that various modifications thereofwill become apparent to those skilled in the art upon reading thespecification. Therefore, it is to be understood that the inventiondisclosed herein is intended to cover such modifications that fallwithin the scope of the appended claims.

1. A hydrocarbyl group substituted carboxylic composition derived from(A) an olefinically unsaturated hydrocarbon, said hydrocarbon having atleast one allylic hydrogen atom, wherein said hydrocarbon comprises a) ahydrocarbon containing at least 8 carbon atoms or b) a polyolefinderived from homopolymerizing or interpolymerizing C₂₋₂₈ olefin(s) andmixtures thereof, optionally with at least one polyene and (B) anα,β-unsaturated carboxylic compound prepared by reacting (1) an activemethylene compound of the formula

 and (2) a carbonyl compound of the general formula

 wherein R^(a) is H or hydrocarbyl and R^(b) is a member of the groupconsisting of H, hydrocarbyl and

 wherein each R′ is independently R or OR and each R is, independently,H or a hydrocarbyl group; and lower alkyl acetals, ketals, hemiacetalsand hemiketals of the carbonyl compound (2).
 2. The carboxyliccomposition of claim 1 wherein said hydrocarbon is a polyolefin derivedfrom homopolymerizing or interpolymerizing C₂₋₂₈ olefin(s) or mixturesthereof, optionally with at least one polygon.
 3. The carboxyliccomposition of claim 2 wherein the olefinically unsaturated hydrocarbonis a homopolymer derived from olefins containing from 2 to 4 carbonatoms.
 4. The carboxylic composition of claim 3 wherein the polyolefinis a polybutene having {overscore (M)}_(n) ranging from about 300 toabout 5,000.
 5. The carboxylic composition of claim 4 wherein thepolybutene is a polyisobutylene wherein at least about 30% of thepolymeric chains have terminal vinylidene groups.
 6. The carboxyliccomposition of claim 5 wherein at least about 70% of the polymericchains have terminal vinylidene groups.
 7. The carboxylic composition ofclaim 2 wherein the polyolefin is an ethylene-propylene copolymer having{overscore (M)}_(n) ranging from about 300 to about 10,000 and theethylene content ranges from about 25% to about 75% by weight.
 8. Thecarboxylic composition of claim 2 wherein the polyolefin is a terpolymerderived from ethylene, at least one C₃₋₂₈ olefin and a polyene, saidterpolymer having {overscore (M)}_(n) ranging from about 1,000 to about10,000.
 9. The carboxylic composition of claim 8 wherein the polyenecomprises at least one cyclic diene.
 10. The carboxylic composition ofclaim 8 wherein the polyene comprises at least one of dicyclopentadieneand an alkylidene norbornene.
 11. The carboxylic composition of claim 8wherein the ethylene content of the terpolymer ranges from about 25% toabout 85% by weight and the non-conjugated polyene content ranges fromabout 0.5% to about 15% by weight.
 12. The carboxylic composition ofclaim 1 wherein the olefinically unsaturated hydrocarbon has {overscore(M)}_(n) ranging from about 300 to about 10,000.
 13. The carboxyliccomposition of claim 1 wherein the active methylene compound comprises adi-lower alkyl malonate.
 14. The carboxylic composition of claim 13wherein the di-lower alkyl malonate comprises dimethyl malonate, diethylmalonate or methyl ethyl malonate.
 15. The carboxylic composition ofclaim 1 wherein the active methylene compound comprises a lower alkylacetoacetate.
 16. The carboxylic composition of claim 15 wherein thelower alkyl acetoacetate comprises methyl- or ethyl- acetoacetate. 17.The carboxylic composition of claim 1 wherein the carbonyl compound (2)comprises an aldehyde wherein R^(a) is H and R^(b) is H or lower alkyl.18. The carboxylic composition of claim 17 wherein the aldehyde isformaldehyde.
 19. The carboxylic composition of claim 1 wherein thecarbonyl compound (2) comprises a ketone wherein each of R^(a) and R^(b)is a lower alkyl group.
 20. A hydrocarbyl group substituted carboxylicderivative composition prepared by reacting at least one hydrocarbylgroup substituted carboxylic composition according to claim 1 with areactant selected from the group consisting of (a) amines characterizedby the presence within their structure of at least one condensableH—N<group, (b) alcohols, (c) reactive metal or reactive metal compounds,and (d) a combination of two or more of any of (a) through (c), thecomponents of (d) being reacted with the carboxylic compositionsimultaneously or sequentially, in any order.
 21. An additiveconcentrate for preparing lubricating oil and fuel compositionscomprising from about 20% to about 99% by weight of a normally liquid,substantially inert organic diluent and from about 1% to about 80% byweight of at least one carboxylic derivative composition of claim 20.22. An additive concentrate for preparing lubricating oil and fuelcompositions comprising from about 20% to about 99% by weight of anormally liquid, substantially inert organic diluent and from about 1%to about 80% by weight of at least one carboxylic composition ofclaim
 1. 23. A hydrocarbyl group substituted carboxylic compositionderived from (A) an olefinically unsaturated hydrocarbon, saidhydrocarbon having at least one allylic hydrogen atom, and (B) acarbonyl compound having the general formula

 or a lower alkyl hemiacetals thereof, wherein each R′ is independentlyR or OR and each R is, independently, H or a hydrocarbyl group.
 24. Thecarboxylic composition of claim 23 wherein R is independently H or loweralkyl.
 25. The carboxylic composition of claim 24 wherein the carbonylcompound is glyoxylic acid or the hydrate thereof.
 26. The carboxyliccomposition of claim 24 wherein the carbonyl compound is a lower alkylester of glyoxylic acid.
 27. The carboxylic composition of claim 24wherein the carbonyl compound is a lower alkyl hemiacetal of a loweralkyl glyoxylate.
 28. The carboxylic composition of claim 27 wherein thecarbonyl compound is the methyl hemiacetal of methyl glyoxylate.
 29. Ahydrocarbyl group substituted polycarboxylic composition derived from(A) an olefinically unsaturated hydrocarbon said hydrocarbon having atleast one allylic hydrogen atom, and (B) an α,β-unsaturatedpolycarboxylic compound prepared by reacting glyoxylic acid or areactive equivalent thereof with an active methylene compound of theformula

 wherein R′ is selected from R and OR and each R is, independently, H orlower alkyl.
 30. A hydrocarbyl group substituted polycarboxyliccomposition derived from (A) at least one olefinically unsaturatedhydrocarbon having at least one allylic hydrogen atom, wherein saidhydrocarbon comprises a) a hydrocarbon containing a least 8 carbon atomsor b) a polyolefin derived from homopolymerizing or interpolymerizingC₂₋₂₈ olefin(s) or mixtures thereof, optionally with at least onepolyene and (B) an α,β-unsaturated polycarboxylic compound of thegeneral formula

 wherein R^(C) is R;

 and each R is, independently, H or hydrocarbyl.
 31. The carboxyliccomposition of claim 30 wherein the polycarboxylic compound (B) istri(lower alkyl) ethylenetricarboxylate.